Surfactants

ABSTRACT

Disclosed are surfactants represented by the following formula (1): 
                 
 
wherein R 1  represents a branched aliphatic hydrocarbon group, a secondary aliphatic hydrocarbon group or a branched aliphatic acyl group, AO and AO′ each independently represents an oxyalkylene group having 2 to 4 carbon atoms, L represents a group represented by formula (2) to be described below, z stands for a number of from 1 to 10, X represents a hydrogen atom or an ionic hydrophilic group, m stands for a number of from 0 to 1,000, and n stands for a number of from 0 to 1,000. 
                 
 
wherein R 2  and R 3  each independently represents a hydrogen atom or a methyl group, x stands for a number of from 0 to 12, and y stands for a number of 0 or 1. These surfactants do not contain any phenyl ether group considered to have significant effects on the environment, such as a nonylphenyl group, and have performance comparable with reactive surfactants containing one or more phenyl ether groups. Emulsifiers for emulsion polymerization, dispersants for dispersion polymerization and resin modifiers, all of which contain the surfactants, are also disclosed.

TECHNICAL FIELD

This invention relates to reactive surfactants containing a branchedaliphatic hydrocarbon group, a secondary aliphatic hydrocarbon group ora branched aliphatic acyl group, and also to their specificapplications.

BACKGROUND ART

Surfactants have a wide variety of functions such as emulsification,dispersion, cleaning, wetting and foaming. Using these variousfunctions, they have been employed for many years in numerous fields ledby fibers and including paper, rubber, plastics, metals, paints,pigments, civil engineering and construction. Especially in recentyears, there is an increasingly active move toward providingmerchandise, which make use of surfactants, with higher performance.Keeping in step with this move, attentions have also been drawn todrawbacks which surfactants are associated with.

For example, surfactants are contained in products such as paints,printing inks and adhesives, because they are considered to beindispensable upon production or from the standpoint of stabilization ofthe products and working convenience. Upon actually using suchsurfactants-containing products in work such as coating, printing,adhesion or bonding, however, the surfactants are fundamentallyunnecessary and in many instances, rather deteriorate properties such aswaterproofness and oil resistance of coatings, printed surfaces,adhesive films and the like.

Emulsifiers for emulsion polymerization, which are used upon producingpolymers by emulsion polymerization, are known not only to take part inpolymerization-initiating reactions and polymer-forming reactions butalso to affect the mechanical stability, chemical stability, freezingstability, storage stability and the like of the resulting emulsions.Further, they are also known to give significant effects on physicalproperties of the emulsions, such as particle size, viscosity andfoaming potential and, when formed into films, physical properties ofthe films, such as waterproofness, weatherability, adhesion and heatresistance. As problems in such emulsion polymerization, it has beenpointed out that the emulsion-polymerized emulsions are highly foameddue to the emulsifiers contained therein and that physical properties offilms, such as adhesion, waterproofness, weatherability and heatresistance, are lowered. In polymers produced by suspensionpolymerization, similar problems caused by the dispersants for thesuspension polymerization have also been pointed out.

These problems can be attributed to the surfactants still remaining infree forms in the polymers. As a method for lowering the contents ofsuch free surfactants, surfactants which react with polymers duringpolymerization or molding or other forming and do not remain in freeforms in the polymers, that is, so-called reactive surfactants which mayalso be called “polymerizable surfactants” have been developed.

Concerning reactive surfactants, many structures have been proposed.Paying attention to their hydrophobic groups, examples can includesulfosuccinate esters containing hydrocarbon groups disclosed in JP49-46291 B; alkoxylates of allyl- or propenyl-containing,hydrocarbyl-substituted phenols, disclosed in JP 62-100502 A, JP63-23725 A, JP 4-50202 A and JP 4-50204 A; alkoxylates of hydrocarbyl-or acyl-containing glycerin derivatives, disclosed in JP 62-104802 A;formaldehyde-crosslinked, (substituted) phenol derivatives disclosed inJP 62-11534 A; and as hydrophobic groups, alkyl groups derived from anα-olefin oxide, disclosed in JP 63-319035 A and JP 4-50204 A.Incidentally, the term “hydrocarbon or hydrocarbyl group” as used in theabove-described conventional art includes alkyl groups, alkenyl groups,aryl groups, and the like.

Among these reactive surfactants, those containing one or more phenylether groups as hydrophobic groups have found wide-spread utility fortheir excellent properties such as emulsifying property, dispersingproperty, and polymerization-stabilizing property.

In recent years, however, a concern has arisen about a potential problemthat nonyl phenol may show false hormone effects on organisms to disruptthe endocrine system, that is, the so-called endocrine problem hasarisen, so that research have also been conducted in efforts to providereplacements for reactive surfactants containing one or more phenylether groups. However, reactive surfactants containing one or morehydrophobic groups other than phenyl ether groups, for example, generalalkyl groups, alkenyl groups or the like are accompanied by a drawbackin that they are inferior in performance to the reactive surfactantscontaining one or more phenyl ether groups.

An object of the present invention is, therefore, to solve theabove-described conventional problems, and to provide a surfactant whichdoes not contain any phenyl ether group considered to give considerableeffects on the environment, such as nonylphenyl group, and hasperformance comparable with the reactive surfactants containing one ormore phenyl ether groups.

DISCLOSURE OF THE INVENTION

The present inventors, therefore, have proceeded with an extensiveinvestigation and as a result, have found that a reactive surfactantcontaining a branched aliphatic hydrocarbon group or a branchedaliphatic acyl group as a hydrophobic group has performance comparablewith reactive surfactants containing one or more (substituted) phenylether groups and moreover, gives substantially no deleterious effect onthe environment, leading to the completion of the present invention.Described specifically, the present invention provides a surfactantrepresented by the following formula (1):

wherein R¹ represents a branched aliphatic hydrocarbon group, asecondary aliphatic hydrocarbon group or a branched aliphatic acylgroup, AO and AO′ each independently represents an oxyalkylene grouphaving 2 to 4 carbon atoms, L represents a group represented by formula(2) to be described below, z stands for a number of from 1 to 10, Xrepresents a hydrogen atom or an ionic hydrophilic group, m stands for anumber of from 0 to 1,000, and n stands for a number of from 0 to 1,000.

wherein R² and R³ each independently represents a hydrogen atom or amethyl group, x stands for a number of from 0 to 12, and y stands for anumber of 0 to 1.

The present invention also provides an emulsifier for emulsionpolymerization, a dispersant for suspension polymerization and a resinmodifier, all of which comprises the surfactant represented by formula(1).

BEST MODES FOR CARRYING OUT THE INVENTION

The present invention will next be described in detail based on certainembodiments.

In the formula (1), R¹ represents a branched aliphatic hydrocarbongroup, a secondary aliphatic hydrocarbon group or a branched aliphaticacyl group. The branched aliphatic hydrocarbon group or secondaryaliphatic hydrocarbon group is a residual group of its correspondingbranched aliphatic alcohol or secondary aliphatic alcohol.

Examples of such a branched aliphatic alcohol can include isobutylalcohol, tertiary butyl alcohol, isopentyl alcohol, neopentyl alcohol,tertiary pentyl alcohol, isohexanol, 2-methylpentanol, isoheptanol,isooctanol, 2-ethylhexanol, isononanol, 3,4,4-trimethylhexanol,isodecanol, 2-propylheptanol, isoundecanol, isododecanol,2-butyloctanol, isotridecanol, isotetradecanol, isomyristyl alcohol,2-pentylnonanol, isopentadecanol, isohexadecanol, isopalmityl alcohol,2-henxyldecanol, isoheptadecanol, isooctadecanol, isostearyl alcohol,2-heptylundecanol, isononadecanol, isoeicosanol, 2-octyldodecanol,2-nonyltridecanol, 2-decyltetradecanol, 2-undecylpentadecanol,2-dodecylhexadecanol, 2-tridecylheptadecanol, 2-tetradecyloctadecanol,2-pentadecylnonadecanol, 2-hexadecyleicosanol, 1,1-dimethyl-2-propenol,3-methyl-3-butenol, 3-methyl-2-butenol, isohexenol, isoheptenol,isooctenol, isononenol, isodecenol, isoundecenol, isododecenol,isotridecenol, isotetradecenol, isopentadecenol, isohexadecenol,isoheptadecenol, isooctadecenol, isooleyl alcohol, isononadecenol, andisoeicocenol.

Examples of such a secondary aliphatic alcohol can include isopropanol,2-butanol, 2-octanol, secondary decanol, secondary undecanol, secondarydodecanol, secondary tridecanol, isotridecanol, secondary tetradecanol,secondary pentadecanol, secondary hexadecanol, secondary heptadecanol,and secondary octadecanol.

On the other hand, the branched aliphatic acyl group is a residual groupof its corresponding branched fatty acid. Examples of the branchedaliphatic acyl group can include isobutanoic acid, isopentanoic acid,neopentanoic acid, isohexanoic acid, 2-methylpentanoic acid, neohexanoicacid, isoheptanoic acid, neoheptanoic acid, isooctanoic acid,2-ethylhexanoic acid, neooctanoic acid, isonoanoic acid,3,4,4-trimethylhexanoic acid, neononanoic acid, isodecanoic acid,2-propylheptanoic acid, neodecanoic acid, isoundecanoic acid,isododecanoic acid, 2-butyloctanoic acid, isotridecanoic acid,isotetradecanoic acid, isomyristic acid, 2-pentylnonanoic acid,isopentadecanoic acid, isohexadecanoic acid, isopalmitic acid,2-hexyldecanoic acid, isoheptadecanoic acid, isooctadecanoic acid,isostearic acid, 2-heptylundecanoic acid, isononadecanoic acid,isoeicosanoic acid, 2-octyldodecanoic acid, 2-nonyltridecanoic acid,2-decyltetradecanoic acid, 2-undecylpentadecanoic acid,2-dodecylhexadecanoic acid, 2-tridecylheptadecanoic acid,2-tetradecyloctadecanoic acid, 2-pentadecylnonadecanoic acid,2-hexadecyleicosanoic acid, and isooleic acid.

Among these branched aliphatic hydrocarbon groups, secondary aliphatichydrocarbon groups and aliphatic acyl groups, those having 8 to 36carbon atoms are preferred, with those having 10 to 28 carbon atomsbeing more preferred. Further, those having many branches are preferredbecause the emulsifying property, dispersing property,polymerization-stabilizing property and the like of a surfactant areimproved with the number of branches. In particular, those having 3 ormore methyl groups per molecule are preferred. Hydrocarbon groups oracyl groups having such many branches may include hydrocarbon or acylgroups each of which is in the form of a mixture of many structuralisomers like commercial isotridecanol. In the case of each of suchhydrocarbon or acyl groups, the number of methyl groups in a moleculecan be determined by a spectrochemical analysis method such as ¹H-NMR.

In the formula (1), the (AO)_(m) and (AO′)_(n) moieties can each beobtained by addition polymerization or the like of an alkylene oxidehaving 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide,butylene oxide or tetrahydrofuran (1,4-butylene oxide). When (AO)_(m)and (AO′)_(n) are each formed by addition polymerization of an alkyleneoxide, (AO)_(m) and (AO′)_(n) are each determined by the alkylene oxideso added. No limitation is imposed on the manner of polymerization ofthe alkylene oxide, so that the polymerization can be homopolymerizationof an alkylene oxide, or random copolymerization, blockcopolymerization, random/block copolymerization or the like of two ormore alkylene oxides. The polymerization degree m is a number in therange of from 0 to 1, 000 and, when X is a hydrogen atom, may rangepreferably from 1 to 200, more preferably from 3 to 100, still morepreferably from 10 to 50. When X is an ionic hydrophilic group, thepolymerization degree may range preferably from 1 to 200, morepreferably from 2 to 100, still more preferably from 2 to 50.

As AO, an oxyethylene group is most preferred. When AO is formed of twoor more types of groups, one type of group(s) may preferably beoxyethylene group(s), and the (AO)_(m) moiety may be a polyoxyalkylenechain containing preferably 50 to 100 mole %, more preferably 60 to 100mole % of oxyethylene groups.

AO′, on the other hand, may preferably be an oxyethylene group from thestandpoint of the availability of its raw material when R¹ is asecondary aliphatic hydrocarbon group. When R¹ is a branched aliphatichydrocarbon group, secondary aliphatic hydrocarbon group or branchedaliphatic acyl group having about 3 to 10 carbon atoms, AO′ maypreferably be an oxyalkylene group having 3 or 4 carbon atoms. Thepolymerization degree n is a number in the range of from 0 to 1,000, andmay range preferably from 0 to 100, more preferably from 0 to 50, stillmore preferably from 0 to 30. Especially when R¹ is a branched aliphatichydrocarbon group, secondary aliphatic hydrocarbon group or branchedaliphatic acyl group having about 3 to 10 carbon atoms, thepolymerization degree n may range preferably from 2 to 30. Thehydrophilic property or hydrophobic property of the surfactantrepresented by the formula (1) can be adjusted by the numbers m and n.It is preferred to adjust m and n to appropriate polymerization degreesdepending on the application purpose.

In the formula (1), L represents a group of the following formula (2).The group represented by formula (2) is a reactive group in thesurfactant of the present invention.

wherein R² and R³ each independently represents a hydrogen atom or amethyl group, x stands for a number of from 0 to 12, and y stands for anumber of 0 or 1.

Illustrative of the group represented by the formula (2) are alkenylgroups such as vinyl, 1-propenyl, allyl, methallyl, 2-butenyl,3-butenyl, 4-pentenyl, 3-methyl-3-butenyl, 5-hexenyl, 8-nonenyl and10-dodecenyl; and unsaturated acyl groups such as acryl, methacryl,2-butenoyl, 3-methyl-3-butenoyl and 2-dodecenoyl. Of these, allyl,methallyl, acryl and methacyl are preferred for the availability andreactivity of their raw materials. Further, groups represented by theformula (2) can be copolymerized (radical polymerization or ionicpolymerization) with other radically-polymerizable, reactive groups. Inaddition, they can also be reacted with a compound containing a groupother than a polymerizable reactive group such as an organopolysiloxanecontaining an Si—H group.

In the formula (1), z stands for a number of from 1 to 10. Depending onthe production process or the like, the surfactant may be obtained inthe form of a mixture of compounds having different z numbers. In thecase of such a mixture, z indicates an average number. As the number zbecomes closer to 1, the surfactant of the present invention tends to bemore improved in emulsifying property, dispersing property,polymerization-stabilizing property and the like. When importance isplaced on emulsifying property, dispersing property,polymerization-stabilizing property and the like, the preferred numberof z can range from 1 to 8, with the number of from 1 to 5 being morepreferred, and the number of from 1 to 3 being most preferred.

When z is a number greater than 1, there is a tendency that emulsionpolymerization or suspension polymerization making use of the surfactantaccording to the present invention can provide the resulting resin withimproved waterproofness and mechanical strength. A z number greater than10, however, leads to lower polymerization-stabilizing property inemulsion polymerization or suspension polymerization and, for example,to more readily occurrence of agglomerates during the polymerizationreaction. Therefore, z is preferably a number greater than 1 whenimportance is placed on the waterproofness and mechanical property of aresin. When the surfactant of the present invention is a mixture ofcompounds the z numbers of which are 1 and 2 or greater, respectively, zcan range preferably from 1.1 to 8 on average.

In the formula (1), X represents a hydrogen atom or an ionic hydrophilicgroup. Illustrative of the ionic hydrophilic group are anionichydrophilic groups and cationic hydrophilic groups. Examples of theanionic hydrophilic groups out of these ionic hydrophilic groups caninclude —SO₃M, —R⁴—SO₃M, —R⁵—COOM, —PO₃M₂, —PO₃ MH and —CO—R⁶—COOM.

In the above-described formulas which represent the anionic hydrophilicgroups, respectively, M represents a hydrogen atom; an alkali metal atomsuch as lithium, sodium or potassium; an alkaline earth metal atom suchas magnesium or calcium, with a proviso that the number of M is ½ sincean alkaline earth metal is generally divalent; or an ammonium ion.Illustrative of the ammonium ion are an ammonium ion available fromammonia; ammonium ions available from alkylamines such asmonomethylamine and dipropylamine; and ammonium ions available fromalkanolamines such as monoethanolamine, diethanolamine andtriethanolamine.

R¹ and R⁵ each independently represents an alkylene group such asmethylene, ethylene, propylene, butylene, pentene, pentamethylene orhexamethylene. Among these, alkylene groups having 1 to 4 carbon atoms,such as methylene, ethylene, propylene and butylene, are preferred fromthe availability of raw materials.

R⁶ represents a residual group obtained by eliminating the carboxylgroups from a dibasic acid or an anhydride thereof. Examples of thedibasic acid can include oxalic acid, malonic acid, succinic acid,glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid,sebacic acid, undecanoic diacid, dodecanoic diacid, tridecanoic diacidand tetradecanoic diacid; saturated alicyclic dicarboxylic acids such ascyclopentanedicarboxylic acid, hexahydrophthalic acid andmethylhexahydrophthalic acid; aromatic dicarboxylic acids such asphthalic acid, isophthalic acid, terephthalic acid, tolyenedicarboxylicacid and xylylenedicarboxylic acid; unsaturated aliphatic dicarboxylicacids such as maleic acid, fumaric acid, itaconic acid, citraconic acidand mesaconic acid; and unsaturated alicyclic dicarboxylic acids such astetrahydrophthalic acid, methyltetrahydrophthalic acid, nadic acid(endomethylenetetrahydrophthalic acid), methylnadic acid,methylbutenyltetrahydrophthalic acid andmethylpentenyltetrahydrophthalic acid. At the production stage, they maybe used in the form of anhydrides.

Among these anionic hydrophilic groups, groups represented by—SO₃M₁—PO₃M₃ and —PO₃ MH are preferred.

X can also be a cationic hydrophilic group. Illustrative of the cationichydrophilic group are those represented by —R⁷—NR⁸R⁹R¹⁰ .Y or-Z-NR⁸R⁹R¹⁰.Y. In these formulas representing cationic hydrophilicgroups, Y represents a halogen atom or a methylsulfuric group (—CH₃SO₄).Examples of the halogen atom can include a chlorine atom, bromine atomand iodine atom. On the other hand, R⁷ represents an alkylene grouphaving 1 to 4 carbon atoms. Illustrative of the alkylene group having 1to 4 carbon atoms are alkylene groups similar to those exemplified abovein connection with the anionic hydrophilic group R⁴.

R⁸, R⁹ and R¹⁰ each independently represents an alkyl group having 1 to4 carbon atoms, an alkanol group having 2 to 4 carbon atoms, or a benzylgroup. Examples of the alkyl group having 1 to 4 carbon atoms caninclude methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondarybutyl, and tertiary butyl. Examples of the alkanol group having 2 to 4carbon atoms, on the other hand, can include 2-hydroxyethyl,2-hydroxypropyl and 2-hydroxybutyl. Further, Z is a group represented by—CH₂CH(OH)CH₂— or —CH(CH₂OH)CH₂—.

No particular limitation is imposed on the process for the production ofthe surfactant represented by the formula (1). Where X is a hydrogenatom, for example, (a) the surfactant can be obtained by adding, in amanner known per se in the art, m moles of an alkylene oxide to areaction product between a glycidyl ether or glycidyl ester containing areactive group represented by the formula (2) and a branched aliphaticalcohol, a secondary aliphatic alcohol, a branched fatty acid or thelike. As an alternative, (b) it can also be obtained by reacting, in amanner known per se in the art, m moles of an alkylene oxide to areaction product between the glycidyl ether of a branched aliphaticalcohol or secondary aliphatic alcohol or the glycidyl ester of abranched fatty acid and an alcohol or carboxylic acid containing areactive group represented by the formula (2). To confirm the completionof the reaction between the glycidyl ether or glycidyl ester and thealcohol or carboxylic acid, an IR absorption or epoxy equivalent, forexample, can be measured to ascertain the end point. In theabove-described production process (a), the branched aliphatic alcohol,secondary aliphatic alcohol or branched fatty acid may still remainunreacted in the reaction product between the glycidyl ether or glycidylester containing the reactive group represented by the formula (2) andthe branched aliphatic alcohol, the secondary aliphatic alcohol, thebranched fatty acid or the like. If this is found to be the case, thealkylene oxide may be added subsequent to removal of such an unreactedalcohol or acid as needed.

In the above-described production, a catalyst can also be used asneeded. No particular limitation is imposed on the catalyst insofar asit is one commonly employed in ring-opening reactions of epoxycompounds. Illustrative are tertiary amines, quaternary ammonium salts,boron trichloride or its ether complexes, aluminum chloride, bariumoxide, sodium hydroxide, and potassium hydroxide.

No particular limitations are imposed on reaction conditions upon addingthe alkylene oxide. In general, the reaction temperature and pressurecan be set at room temperature to 150° C. and 0.01 to 1 MPa,respectively, and if necessary, sodium hydroxide, potassium hydroxide,boron trifluoride or the like can be used as a catalyst. Where X is anionic hydrophilic group, the compound obtained through theabove-described reaction is subjected further to a reaction such thatthe ionic hydrophilic group can be introduced.

When conversion into a sulfate ester is conducted to introduce ananionic hydrophilic group represented by —SO₃M out of the formulasrepresenting ionic hydrophilic groups, it is possible to use, forexample, sulfamic acid, sulfuric acid, sulfuric anhydride, fumingsulfuric acid, chlorosulfonic acid or the like as an anionichydrophilizing agent. No particular limitation is imposed on reactionconditions upon conducting the conversion into a sulfate ester, but ingeneral, the reaction can be conducted at a temperature of from roomtemperature to 150° C. under environmental pressure or an elevatedpressure up to about 0.5 MPa for approximately 1 to 10 hours.

When an anionic hydrophilic group represented by —R⁴—SO₃M is introducedout of the formulas representing ionic hydrophilic groups, it ispossible to use, for example, propanesultone, butanesultone or the likeas an anionic hydrophilizing agent. No particular limitation is imposedon reaction conditions upon sulfonation, but in general, the reactioncan be conducted at a temperature of from room temperature to 100° C.under environmental pressure or an elevated pressure up to about 0.5 MPafor approximately 1 to 10 hours. An alkali such as sodium hydroxide orpotassium hydroxide may be used as a catalyst as needed. Further, asolvent may be added as needed.

When carboxylation is conducted to introduce an anionic hydrophilicgroup represented by —R⁵—COOM out of the formulas representing ionichydrophilic groups, it is possible to use, for example, chloroaceticacid (R⁵: methyl), chloropropionic acid (R⁵: ethyl), a salt thereof orthe as an anionic hydrophilizing agent. No particular limitation isimposed on reaction conditions upon conducting the carboxylation, but ingeneral, the carboxylation can be conducted at a temperature of fromroom temperature to 150° C. under environmental pressure or an elevatedpressure up to about 0.5 MPa for approximately 1 to 10 hours. An alkalisuch as sodium hydroxide or potassium hydroxide may be used as acatalyst as needed.

When conversion into a phosphate ester is conducted to introduce ananionic hydrophilic group represented by —PO₃M₂ or —PO₃ MH out of theformulas representing ionic hydrophilic groups, it is possible to use,for example, diphosphorus pentoxide, polyphosphoric acid,orthophosphoric acid, phoshorus oxychloride or the like as an anionichydrophilizing agent. The conversion into a phosphate ester a monoestercompound and a diester compound are obtained as a mixture. They may beseparated from each other. If their separation is difficult, however,they may be used as are, that is, in the form of the mixture. Noparticular limitation is imposed on reaction conditions upon conductingthe conversion into a phosphate ester, but in general, the reaction canbe conducted at a temperature of from room temperature to 150° C. underenvironmental pressure for approximately 1 to 10 hours.

When conversion into a dibasic acid is conducted to introduce an anionichydrophilic group represented by —CO—R⁶—COOM out of the formulasrepresenting ionic hydrophilic groups, it is possible to use, forexample, the above-mentioned dibasic acid or an anhydride thereof as ananionic hydrophilizing agent. Illustrative are maleic acid (R⁶: CH═CH),phthalic acid (R⁶: phenyl), and salts or anhydrides thereof. Noparticular limitation is imposed on reaction conditions upon conductingthe conversion into a dibasic acid, but in general, the reaction can beconducted at a temperature of from room temperature to 150° C. underenvironmental pressure for approximately 1 to 10 hours. An alkali suchas sodium hydroxide or potassium hydroxide may be used as a catalyst asneeded.

When anionic hydrophilization is conducted, post-neutralization may beconducted with an alkali such as sodium hydroxide or potassiumhydroxide, ammonia, an alkylamine, or an alkanolamine such asmonoethanolamine or diethanolamine.

When introducing a cationic hydrophilic group represented by—R¹—NR⁸R⁹R¹⁰ Y out of the formulas representing ionic hydrophilicgroups, the cationic hydrophilic group can be introduced by firstlyhalogenating the hydroxyl group of a compound represented by the formula(1), in which X is a hydrogen atom, with a halogenating agent such asthionyl chloride, thionyl bromide or phosgene and then reacting atertiary amine compound. As an alternative, a secondary amine compoundcan be reacted in place of a tertiary amine compound, followed by areaction with an alkyl halide, dimethyl sulfate or the like. Noparticular limitation is imposed on reaction conditions uponhalogenating the hydroxyl group, but in general, the halogenation can beconducted at a temperature of from room temperature to 100° C. underenvironmental pressure or an elevated pressure up to about 0.5 MPa forapproximately 1 to 10 hours. No particular limitation is imposed eitherupon amination, but in general, the amination can be conducted at atemperature of from room temperature to 150° C. under environmentalpressure or an elevated pressure up to about 0.5 MPa for approximately 1to 10 hours. An alkali such as sodium hydroxide or potassium hydroxidemay be used as a catalyst as needed.

When introducing a cationic hydrophilic group represented by-Z-NR⁸R⁹R¹⁰—Y out of the formulas representing ionic hydrophilic groups,the cationic hydrophilic group can be introduced by firstly reacting anepihalohydrin such as epichlorohydrin or epibromohydrin with a compoundrepresented by the formula (1), in which X is a hydrogen atom, and thenfurther reacting a tertiary amine compound. As an alternative, asecondary amine compound can be reacted in place of a tertiary aminecompound, followed by a reaction with an alkyl halide, dimethyl sulfateor the like. No particular limitation is imposed on reaction conditionsupon reacting the epihalohydrin, but in general, the reaction can beconducted at a temperature of from room temperature to 100° C. underenvironmental pressure or an elevated pressure up to about 0.3 MPa forapproximately 1 to 10 hours. An alkali catalyst such as sodium hydroxideor potassium hydroxide or an acid catalyst such as sulfuric acid,phosphoric acid, iron chloride, boron fluoride or tin chloride may beused as needed. No particular limitation is imposed either uponamination, but in general, the amination can be conducted at atemperature of from room temperature to 150° C. under environmentalpressure or an elevated pressure up to about-0.5 MPa for approximately 1to 10 hours. An alkali such as sodium hydroxide or potassium hydroxidemay be used as a catalyst as needed.

Surfactants according to the present invention can be used forapplications in which reactive surfactants containing one or more phenylether groups have been used to date, specifically as emulsifiers foremulsion polymerization, dispersants for suspension polymerization,resin modifiers (for improvements in water repellency, adjustments inhydrophilicity, improvements in antistatic properties, improvements inanti-fogging properties, improvements in waterproofness, improvements inadhesion properties, improvements in dyeability, improvements infilm-forming properties, improvements in weatherability, improvements inanti-blocking properties, etc.), fiber processing aids, non-drippingagents, soil resistance finishes, and the like. They can also be used asraw materials for copolymerizable surfactants (for example, thosedisclosed in JP 10-120712 A, etc.) and raw materials forsurfactant-modified organopolysiloxanes (for example, those disclosed inJP 6-65379 A, etc.

When any one of the surfactants according to the present invention isused as an emulsifier for emulsion polymerization, it can be used in anydesired proportion within a proportion range in whichconventionally-known emulsifiers for emulsion polymerization are usedordinarily. In general, however, it can be used preferably in aproportion of from 0.1 to 20 wt. %, more preferably in a proportion offrom 0.2 to 10 wt. % based on the raw material monomer or monomers.Further, the invention emulsifier for emulsion polymerization can beused in combination with another reactive or non-reactive emulsifier.Although no particular limitation is imposed on the monomer(s) to besubjected to emulsion polymerization, the invention emulsifier foremulsion polymerization can be used preferably for acrylate emulsions,styrene emulsions, vinyl acetate emulsions, SBR (styrene/butadiene)emulsion, ABS (acrylonitrile/butadiene/styrene) emulsion, BR (butadiene)emulsion, IR (isoprene) emulsion, NBR (acrylonitrile/butadiene)emulsion, and the like.

Examples of (co)polymerizable monomers in the acrylate emulsions caninclude (meth)acrylic acid (acrylate) alone, (meth)acrylic acid(acrylate)/styrene, (meth)acrylic acid (acrylate)/vinyl acetate,(meth)acrylic acid (acrylate)/acrylonitrile, (meth)acrylic acid(acrylate)/butadiene, (meth)acrylic acid (acrylate)/vinylidene chloride,(meth)acrylic acid (acrylate)/allylamine, (meth)acrylic acid(acrylate)/vinylpyridine, (meth)acrylic acid (acrylate)/alkylolamides,(meth)acrylic acid (acrylate)/N,N-dimethylaminoethyl esters, and(meth)acrylic acid (acrylate)/N,N-diethylaminoethyl vinyl ether.

Examples of (co)polymerizable monomers in the styrene emulsions caninclude, in addition to styrene alone, styrene/acrylonitrile,styrene/butadiene, styrene/fumaronitrile, styrene/maleonitrile,styrene/cyanoacrylate esters, styrene/phenylvinyl acetate,styrene/chloromethylstyrene, styrene/dichlorostyrene,styrene/vinylcarbazole, styrene/N,N-diphenylacrylamide,styrene/methylstyrene, acrylonitrile/butadiene/styrene,styrene/acrylonitrile/methylstyrene,styrene/acrylonitrile/vinylcarbazole, and styrene/maleic acid.

Examples of (co)polymerizable monomers in the vinyl acetate emulsionscan include, in addition to vinyl acetate alone, vinyl acetate/styrene,vinyl acetate/vinyl chloride, vinyl acetate/acrylonitrile, vinylacetate/maleic acid (maleates), vinyl acetate/fumaric acid (fumarates),vinyl acetate/ethylene, vinyl acetate/propylene, vinylacetate/isobutylene, vinyl acetate/vinylidene chloride, vinylacetate/cyclopentadiene, vinyl acetate/crotonic acid, vinylacetate/acrolein, and vinyl acetate/alkyl vinyl ethers.

When any one of the surfactants according to the present invention isused as a dispersant for suspension polymerization, it can be used inany desired proportion within a proportion range in whichconventionally-known dispersants for suspension polymerization are usedordinarily. In general, however, it can be used preferably in aproportion of from 0.1 to 20 wt. %, more preferably in a proportion offrom 0.2 to 10 wt. % based on the raw material monomer or monomers.Further, the invention dispersant for suspension polymerization can beused in combination with another reactive or non-reactive dispersant,for example, polyvinyl alcohol or the like. No particular limitation isimposed on the monomer(s) to be subjected to suspension polymerization,and the invention dispersant for suspension polymerization can be usedfor the homopolymerization or copolymerization of the above-describedmonomers each having one or more polymerizable carbon—carbon doublebonds. Preferably, the invention dispersant for suspensionpolymerization can be used for the homopolymerization orcopolymerization of halogenated olefinic monomers, vinyl acetatemonomers and the like.

Examples of the halogenated olefinic monomers can include vinylchloride, vinylidene chloride, vinyl chloride/maleic acid (maleates),vinyl chloride/fumaric acid (fumarates), vinyl chloride/vinyl acetate,vinyl chloride/vinylidene chloride, vinylidene chloride/vinyl acetate,and vinylidene chloride/vinyl benzoate.

When the surfactants according to the present invention are used asresin modifiers, physical properties to be modified are, for example,hydrophilicity, compatibility, antistatic properties, anti-foggingproperties, adhesion properties, dyeability, film-forming properties,weatherability, and anti-blocking properties. No particular limitationis imposed on the resin to be modified, and the surfactants according tothe present invention can be used for all polymers available from(co)polymerization of the above-described monomers. In addition, thesurfactants according to the present invention can also be used, forexample, for polyester resins, polyamide resins, polyimide resins,polyaryl ether resins, epoxy resins, and urethane resins. Resins whichcan be used particularly preferably are polyhalogenated olefins such asvinyl chloride and vinylidene chloride; and poly (α-olefins) such asethylene and propylene.

The resin modifiers according to the present invention can be added toresins, for example, by coating them onto surfaces of the resins orincorporating them in the resins with kneading. When any one of theresin modifiers according to the present invention is polymerized as oneof monomer components with the remaining monomer (s), the resin modifieraccording to the present invention is incorporated in the molecule ofthe resulting resin such that permanent modification effects such aspermanent antistatic properties can be obtained.

As each resin modifiers according to the present invention containsether chains in its chemical structure, it exhibits superb compatibilitywith monomers. When it contains AO and AO′, its hydrophilicity can beeasily adjusted by choosing the polymerization degrees (m and n) of theoxyalkylene groups and the kinds of the oxyalkylene groups as desireddepending on the purpose of the modification and its compatibility withthe monomer(s). The resin modifier according to the present invention,therefore, can be improved in its compatibility with monomer(s) and itspolymer modifying effects at the same time. Use of the resin modifieraccording to the present invention in a resin can also impart permanentantistatic properties and anti-fogging properties to the resin.

The proportion of each resin modifier according to the present inventioncan be widely changed depending on the kind(s) of monomer(s), thepurpose of a modification, the required performance, and so on.Preferably, however, the resin modifier can be used in a proportion offrom 0.1 to 80 wt. % based on the monomer(s). Especially when desired toconvert a water-soluble resin of insufficient hydrophilicity into aresin of high hydrophilicity, it is more preferred to use the resinmodifier in a proportion of from 1 to 80 wt. % based on the monomer(s).When employed for other purposes, for example, to improvewaterproofness, adhesion properties, antistatic properties, anti-foggingproperties, dyeability, film-forming properties, weatherability,anti-blocking properties and the like or to impart compatibility topolymers for a polymer alloy, the resin modifier can be used preferablyin a proportion of from 0.1 to 60 wt. % based on the monomer(s).

When the resin modifiers according to the present invention are used inresins, a crosslinkable divinyl compound—such as divinyl benzene,ethylene glycol dimethacrylate or methylene bisacrylamide—or the likecan be used in a desired proportion within an ordinary proportion rangeto improve physical properties of the resins. Further, when employed asemulsifiers for emulsion polymerization, as dispersants for suspensionpolymerization or as resin modifiers, existence of a metallic oxidizingagent, for example, makes it possible to induce crosslinking of theresulting resin polymers.

EXAMPLES

The present invention will hereinafter be described in further detailbased on Examples, in which all designations of “%” and “part(s)” are ona weight basis unless otherwise specifically indicated.

Production Example 1

Into a 3-L, stainless steel autoclave equipped with a stirrer, athermometer and a nitrogen inlet tube, isotridecanol [the number ofmethyl groups: 4.3 (as measured by ¹H-NMR)] (1.000 g, 5 moles) and as acatalyst, sodium hydroxide (10 g) were charged. After replacing theinternal atmosphere of the reactor with nitrogen, allyl glycidyl ether(570 g, 5 moles) was fed at 90° C. Subsequent to completion of thefeeding, the reaction product was allowed to age at 90° C. for 5 hoursto obtain a compound (A). To the compound (A) (942 g, 3 moles), ethyleneoxide (1,320 g, 30 moles) was fed at 130° C. Subsequent to completion ofthe feeding, the reaction product was allowed to age for 2 hours toafford a surfactant (1) according to the present invention.

Production Example 2

To the surfactant (1) (377 g, 0.5 mole), ethylene oxide (440 g, 10moles) was fed further at 130° C. Subsequent to completion of thefeeding, the reaction product was allowed to age for 2 hours to afford asurfactant (2) according to the present invention.

Production Example 3

In a 500-mL, 4-necked glass flask equipped with a stirrer, a thermometerand a nitrogen inlet tube, the compound (A) (157 g, 0.5 mole) wasplaced, followed by cooling to 0 to 5° C. In to the compound (A) socooled, chlorosulfonic acid (115 g) was added dropwise through adropping funnel. After the dropwise addition, stirring was conducted for1 hour at the same temperature, and produced HCl was eliminated byblowing nitrogen. The resulting product was then neutralized into thesodium salt with an aqueous solution of sodium hydroxide to afford asurfactant (3) according to the present invention.

Production Example 4

In a similar manner as in Production Example 3, the surfactant (1) wastreated with chlorosulfonic acid to convert it into a sulfate ester,followed by neutralization with an aqueous solution of ammonia to yielda surfactant (4) according to the present invention.

Production Example 5

In a similar flask as in Production Example 3, the surfactant (1) (452g, 0.6 mole) was placed. After diphosphorus pentoxide (28.4 g, 0.6 mole)was added at 40° C. over 1 hour, aging was conducted at 80° C. for 2hours. Subsequently, the reaction mixture was neutralized with anaqueous solution of sodium hydroxide to yield a surfactant (5) accordingto the present invention.

Production Example 6

In a similar flask as in Production Example 3, the surfactant (1)yielded in Production Example 1 (377 g, 0.5 mole) and maleic anhydride(49 g, 0.5 mole) were placed, followed by stirring at 80° C. to conductesterification. The reaction mixture was then neutralized with anaqueous solution of potassium hydroxide to yield a surfactant (6)according to the present invention.

Production Example 7

In a similar autoclave as in Production Example 1, the surfactant (1)(377 g, 0.5 mole) was placed. Under similar conditions as in ProductionExample 1, a mixture of ethylene oxide (440 g, 10 moles) and propyleneoxide (290 g, 5 moles) were then reacted to yield a surfactant (7)according to the present invention.

Production Example 8

In a similar flask as in Production Example 3, the surfactant (1) (377g, 0.5 mole) and boron trifluoride-ethyl ether complex (5 g) wereplaced, and epichlorohydrin (38 g, 0.5 mole) was added dropwise to reactit with the surfactant (1). The reaction product was then reacted withtriethanolamine (75 g, 0.5 mole) to introduce an ammonium ion, whereby asurfactant (8) according to the present invention was yielded.

Production Examples 9 and 10

Following the procedures of Production Examples 1 and 2 except that5,7,7-trimethyl-2-(1,3,3-trimethylbutyl)octanol (number of methylgroups: 8) and methallyl glycidyl ether were used in place ofisotridecyl alcohol and allyl glycidyl ether, respectively, surfactants(9) and (10) according to the present invention were obtained.

Production Example 11

In a similar manner as in Production Example 3, the surfactant (9) wastreated with chlorosulfonic acid to convert it into a sulfate ester,followed by neutralization with potassium hydroxide to yield asurfactant (11) according to the present invention.

Production Example 12

Into a 3-L, 4-necked glass flask equipped with a stirrer, a thermometerand a nitrogen inlet tube, “SOFTANOL 30” [trade name, product of NipponShokubai Co., Ltd.; adduct of 3 moles of ethylene oxide with a secondaryalcohol having 12 to 14 carbon atoms (number of methyl groups: 2),hydroxyl number: 168 mgKOH/g; 668 g, 2 moles] and borontrifluoride.ethyl ether complex (5 g) were charged. At temperatures offrom 30 to 80° C., epichlorohydrin (153 g, 2 moles) was added dropwiseover 1 hour, followed by aging at 80° C. for 2 hours. Subsequently, 48%sodium hydroxide (250 g, 3 moles) was added dropwise at 80° C. over 30minutes. After completion of the dropwise addition, aging was conductedat 80° C. for 2 hours. Toluene (800 g) was then added as a solvent, andthe resulting mixture was washed three times with water (1,000 g×3). Thethus-washed mixture was then heated under reduced pressure to drive offtoluene, whereby a compound (B) was yield.

Into a similar autoclave as in Production Example 1, allyl alcohol (108g, 2 moles) and as a catalyst, potassium oxide (4.8 g) were charged.After replacing the internal atmosphere of the autoclave with nitrogen,the compound (B) (256 g, 1 mole) was fed at 90° C. After completion ofthe feeding, aging was conducted at 90° C. for 5 hours. Subsequently,excess allyl alcohol was distilled off under reduced pressure. Thepressure of the autoclave was then raised back to environmental pressurewith nitrogen, and at 130° C., propylene oxide (290 g, 5 moles) andthen, ethylene oxide (440 g, 10 moles) were fed. Subsequent tocompletion of the feeding, aging was conducted for 2 hours to yield asurfactant (12) according to the present invention.

Production Example 13

In a similar manner as in Production Example 5, the surfactant (12) wastreated with diphosphorus pentoxide to convert it into a phosphateester, followed by neutralization with potassium hydroxide to yield asurfactant (13) according to the present invention.

Production Example 14

Following the procedure of Production Example 1 except that methacrylglycidyl ester was used in lieu of allyl glycidyl ether, borontrifluoride ethyl ether complex was employed as a catalyst instead ofsodium hydroxide, and a mixture of ethylene oxide and tetrahydrofuranwas used in place of ethylene oxide, a surfactant (14) according to thepresent invention was yielded.

Production Example 15

In a similar manner as in Production Example 3, the surfactant (14) wastreated with chlorosulfonic acid to convert it into a sulfate ester,followed by neutralization with sodium hydroxide to yield a surfactant(15) according to the present invention.

Production Example 16

Following the procedure of Production Example 1 except thatisotridecanoic acid (number of methyl groups: 4.3 as measured by ¹H-NMR)was employed in lieu of isotridecyl alcohol and boron trifluoride-ethylether complex was used as a catalyst instead of sodium hydroxide, asurfactant (16) according to the present invention was yielded.

Production Example 17

Following the procedures of Production Examples 1 and 4 except thatisoundecyl alcohol (number of methyl groups: 3.5 as measured by ¹H-NMR)was employed in lieu of isotridecyl alcohol, a surfactant (17) accordingto the present invention was yielded.

Production Example 18

Following the procedure of Production Example 1 except that the amountof allyl glycidyl ether was increased from 570 g (5 moles) to 1,140 g(10 moles), a surfactant (18) according to the present invention wasyielded. Incidentally, the surfactant (18) corresponds to the formula(1) in which z is 2.

Production Example 19

Following the procedure of Production Example 1 except that isoundecylalcohol (860 g, 5 moles) was used instead of isotridecanol (1,000 g, 5moles) and the amount of allyl glycidyl ether was increased from 570 g(5 moles) to 855 g (7.5 moles), a surfactant (19) according to thepresent invention was yielded. Incidentally, the surfactant (19)corresponds to the formula (1) in which z is 1.5.

Production Example 20

Following the procedure of Production Example 4 except that thesurfactant (19) was used in place of the surfactant (1), a surfactant(20) according to the present invention was yielded.

Production Example 21

Following the procedure of Production Example 5 except that thesurfactant (19) was used in place of the surfactant (1), a surfactant(21) according to the present invention was yielded.

Production Example 22

Following the procedures of Production Examples 19 and 20 except thatthe amount of allyl glycidyl ether was increased from 855 g (7.5 moles)to 1,710 g (15 moles), a surfactant (22) according to the presentinvention was yielded. Incidentally, the surfactant (22) corresponds tothe formula (1) in which z is 3.

Production Example 23

Into a 3-L stainless steel autoclave equipped with a stirrer, athermometer and a nitrogen inlet tube, isoundecanol (172 g, 1 mole) andas a catalyst, sodium hydroxide (2 g) were charged. After replacing theinternal atmosphere of the autoclave with nitrogen, allyl glycidyl ether(171 g, 1.5 moles) was fed at 90° C. Subsequent to completion of thefeeding, aging was conducted at 90° C. for 5 hours. Butylene oxide (360g, 5 moles) was then fed at 130° C., and after completion of thefeeding, aging was conducted for 2 hours to yield a surfactant (23)according to the present invention. Incidentally, the surfactant (23)corresponds to the formula (1) in which z is 1.5.

Production Example 24

A 1:1 mixture in terms of weight ratio of the surfactant (17) accordingto the present invention and the surfactant (20) according to thepresent invention was provided as a surfactant (24) according to thepresent invention. The surfactant (24) corresponds to the formula (1) inwhich z is 1.2.

The surfactants according to the present invention, which had beenobtained in the above Production Examples, have the following structuralformulas, in which EO represents an oxyethylene group and PO representsan oxypropylene group. Further, THF represents a tetrahydrofuranresidual group (1,4-butylene oxide residual group).

Further, the following comparative products were used in Examples to bedescribed hereinafter.

Comparative Example 1

Comparative Example 2

Comparative Example 3

Comparative Example 4

Example 1

With respect to the surfactants (1) to (24) according to the presentinvention, surface tensions of their aqueous solutions were measured bythe Wilhelmy method. The results are shown in Table 1. The followingtest conditions were employed.

-   -   Measuring condition: 0.1% aqueous solution    -   Measuring temperature: 25° C.

TABLE 1 Invention product Surface tension (mN/m) 1 38.1 2 34.1 3 33.8 433.1 5 35.5 6 35.6 7 37.2 8 38.5 9 35.2 10 36.9 11 34.8 12 35.8 13 36.114 34.5 15 35.7 16 39.1 17 34.4 18 35.2 19 36.3 20 36.1 21 35.1 22 35.223 36.1 24 34.8

Example 2

With respect to the surfactants (1) to (24) according to the presentinvention and the comparative products 1 to 4, their carbon blackdispersing performance and toluene emulsifying performance weremeasured. The results are shown in Table 2. The following testingmethods were employed.

<Testing Method of Carbon Black Dispersing Performance>

In a graduated cylinder of 100 mL capacity with a ground stopper, theabove-described surfactant (1 g) and carbon black (10 g) were placed,and then dissolved and dispersed with water in an amount sufficient toadjust the total volume to 100 mL. The graduated cylinder was shaken 100times in 1 minute, and then allowed to stand at 25° C. for 1 hour.Subsequently, the dispersion was drawn as much as 30 mL from the topsurface of the dispersion and filtered through a glass filter. The glassfilter was then dried at 105° C., and the weight of a residue on theglass filter was measured. Dispersing performance (%) was thencalculated in accordance with the following formula:Dispersing  performance  (%) = {Weight  of  the  residue  on  the  glass  filter  (g)/3  (g)} × 100<Testing Method of Toluene Emulsifying Performance>

Into a graduated test tube of 20 mL capacity with a ground stopper, a0.5% aqueous solution (5 mL) of the above-described surfactant andtoluene (5 mL) were added. The test tube was shaken 100 times in oneminute, and then allowed to stand at 25° C. for 1 hour. Subsequently,the volume (mL) of an emulsified layer was measured, and the emulsifyingperformance (%) was calculated in accordance with the following formula:Emulsifying  performance  (%) = {Volume  of  the  emulsified  layer  (mL)}/10  (mL)} × 100

TABLE 2 Dispersing Emulsifying performance (%) performance (%) Inventionproduct 1 87 90 2 90 85 3 88 89 4 93 91 5 91 88 6 89 85 7 85 83 8 83 859 87 91 10 91 94 11 89 90 12 92 92 13 92 89 14 88 86 15 87 87 16 85 8917 90 91 18 91 89 19 91 88 20 88 90 21 85 85 22 91 88 23 89 91 24 90 92Comp. product 1 69 68 2 71 73 3 85 89 4 86 88

Example 3

With respect to the invention surfactants (1), (12), (16) and (22) andthe comparative products 2 and 4, a biodegradability test was conductedin accordance with the method of JIS-K-0102. BOD is the abbreviation ofbiochemical oxygen demand, and is the amount of dissolved oxygenconsumed by aerobic microorganisms in water. In this test, each BOD isthe amount of dissolved oxygen consumed when the corresponding samplewas diluted with diluent water and then left over at 20° C. for 5 days.On the other hand, each TOD is a specific value determined from thechemical structure of the corresponding sample.

TABLE 3 Percent biodegradation BOD/TOD Invention product 1 15.3 12 17.816 16.4 22 14.3 Comp. prod. 2 19.3 4 0.12

Example 4

With respect to each of the invention surfactants (1) to (24) and thecomparative products 1 to 4, emulsion polymerization was conducted usinga mixture of 2-ethylhexyl acrylate and acrylic acid as monomers todetermine its performance as an emulsifier for emulsion polymerization.Concerning the thus-obtained polymer emulsion, its particle size, amountof agglomerates, mechanical stability and foaming potential weremeasured, and the waterproofness of a film obtained from the polymeremulsion was measured. The results are shown in Table 4.

<Polymerization Process>

Into a reaction vessel equipped with a reflux condenser, a stirrer, adropping funnel and a thermometer, deionized water (120 g) was charged,and the interior of the system was purged with nitrogen gas. On theside, one of the surfactants (1) to (24) and the comparative products 1to 4 (4 g) was dissolved in a mixed monomer (2-ethylhexylacrylate/acrylic acid=97/3 by weight; 100 g). A 10-gram aliquot of themonomer solution and ammonium persulfate (0.08 g) were added to thereaction vessel, and polymerization was initiated at 60° C. Theremaining mixture of the monomers and the surfactant was continuouslyadded dropwise into the reaction vessel over 2 hours. After completionof the dropwise addition, aging was conducted for 2 hours to afford apolymer emulsion.

<Particle Size>

The particle size of the polymer in each of the polymer emulsions afterthe polymerization was measured at 25° C. using an electrophoretic lightscattering spectrophotometer (“ELS-800”; manufactured by OTSUKAELECTRONICS CO., LTD.).

<Amount of Agglomerates>

Each of the polymer emulsions after the polymerization was filteredthrough a 325-mesh screen. The filtration residue was washed with water,and then dried at 105° C. for 2 hours. Its weight was measured andexpressed in terms of weight % based on the solid content in the polymeremulsion.

<Mechanical Stability>

Each of the polymer emulsions after the polymerization was stirred at2,000 rpm for 2 minutes in “T.K. HOMO DISPER”. The amount ofagglomerates was then measured by the above-described method to rank themechanical stability.

<Foaming Potential>

Each of the polymer emulsions after the polymerization was dilutedtwo-fold with water. A 20-mL aliquot of the thus-diluted emulsion wasplaced in a graduated 100-mL test tube, and was violently shaken up anddown for 10 seconds. The volume of foam was measured shortly after theshaking and also 5 minutes later.

<Waterproofness of Film>

Each of the polymer emulsions after the polymerization was coated on aglass plate to form a coating of 0.2 mm in thickness. The glass platewith the coating formed thereon was then immersed in water of 50° C.,and the time until 8-point characters became no longer legible throughthe whitened coating was determined to rank the waterproofness. Thefollowing ranking standard was employed.

-   -   A: The characters were legible even after an elapsed time of 48        hours.    -   B: The characters were legible after an elapsed time of 24        hours, but became no longer legible after an elapsed time of 48        hours.    -   C: The characters became no longer legible after an elapsed time        of 1 hour.    -   D: The characters became illegible in less 1 hour.

TABLE 4 Amount of Mechan- Foaming Particle agglom- ical potential (mL)Water- size erates stability Shortly 5 min. proof- (μm) (%) (%) afterlater ness Invention product 1 0.11 0.05 3.4 29 8 B 2 0.09 0.07 2.0 30 6B 3 0.08 0.03 1.6 27 5 B 4 0.11 0.09 2.3 31 10 B 5 0.14 0.08 3.1 30 7 A6 0.12 0.06 3.7 29 4 B 7 0.11 0.10 3.0 32 11 B 8 0.10 0.02 1.8 33 7 B 90.08 0.04 1.5 28 8 B 10 0.09 0.03 2.1 29 5 B 11 0.12 0.07 3.9 28 4 B 120.15 0.09 3.1 30 7 B 13 0.13 0.03 2.0 26 5 B 14 0.12 0.04 2.8 33 11 A 150.11 0.03 2.5 32 8 A 16 0.12 0.09 3.9 34 7 B 17 0.11 0.09 2.1 33 7 B 180.10 0.08 2.5 31 6 A 19 0.09 0.04 2.9 29 3 B 20 0.13 0.08 2.7 29 5 A 210.11 0.10 2.9 31 7 A 22 0.10 0.11 3.1 33 8 A 23 0.09 0.07 1.8 30 7 B 240.09 0.09 2.7 29 6 B Comp. product 1 0.38 1.30 34.5 33 18 D 2 0.20 0.8029.8 30 15 D 3 0.18 1.10 18.7 32 13 C 4 0.13 0.25 9.0 36 13 C

Example 5

With respect to each of the invention surfactants (1) to (24) and thecomparative products 1 to 4, emulsion polymerization was conducted usinga mixture of ethyl acrylate, butyl acrylate and styrene as monomers todetermine its performance as a dispersant for emulsion polymerization.Concerning the thus-obtained polymer emulsion, concerning thethus-obtained polymer emulsion, its particle size, amount ofagglomerates and mechanical stability were measured, and thewaterproofness and impact resistance of a film obtained from the polymeremulsion were measured. The results are shown in Table 5.

<Polymerization Process>

Polymer emulsions were obtained in a similar manner as in Example 4except that the mixed monomer was a mixture of ethyl acrylate/butylacrylate/styrene at a weight ratio of 49/49/2.

<Impact Resistance>

Each of the polymer emulsions after the polymerization was coated onmild steel plates (200 mm×100 mm×4 mm) to prepare specimens each ofwhich had a coating of 0.5 mm in thickness. With respect to thespecimens, an impact resistance test was conducted following the chiptest A in JIS-K-5400 (General Testing Methods for Paints). Incidentally,the test was conducted ten times and each of the specimens was visuallyobserved for possible cracking or chipping of its coating caused by animpact of a weight (falling steel ball). The impact resistance wasranked in accordance with the following standard:

-   -   A: Neither cracking nor chipping by the weight was observed, or        cracking or chipping by the weight was observed once.    -   B: Cracking or chipping by the weight was observed twice or        three times.    -   C: Cracking or chipping by the weight was observed four times or        more.

TABLE 5 Amount of Particle agglom- Mechanical size erates stabilityWater- Impact (μm) (%) (%) proofness resistance Invention product 1 0.100.09 18.3 B B 2 0.08 0.08 15.7 B B 3 0.09 0.04 18.5 B B 4 0.10 0.08 17.3B A 5 0.16 0.08 17.8 B B 6 0.10 0.06 16.9 A A 7 0.13 0.11 15.1 B B 80.11 0.06 16.1 B B 9 0.09 0.07 18.5 B B 10 0.07 0.05 17.6 B B 11 0.110.08 18.9 B B 12 0.17 0.10 17.1 B B 13 0.13 0.04 15.7 B A 14 0.10 0.0516.6 B A 15 0.15 0.09 18.8 B A 16 0.11 0.12 19.5 B B 17 0.08 0.07 18.2 BB 18 0.09 0.08 17.1 A A 19 0.11 0.08 20.1 B A 20 0.09 0.10 18.9 A A 210.10 0.09 17.1 A A 22 0.16 0.12 20.3 A A 23 0.14 0.11 15.1 A A 24 0.090.09 19.7 A A Comp. product 1 0.26 1.60 42.1 C C 2 0.15 1.20 38.3 C B 30.26 1.19 21.5 C C 4 0.13 0.30 19.9 B C

Example 6

With respect to each of the invention surfactants (1) to (7), (9) to(13) and (17) to (24) and the comparative products 1 to 4, suspensionpolymerization was conducted using vinyl chloride as a monomer todetermine its performance as a dispersant for suspension polymerization.Concerning the thus-obtained polymer, tests were conducted in accordancewith the following testing methods. The results are shown in Table 6.

<Polymerization Process>

Into a 500-mL stainless steel autoclave equipped with a stirrer, athermometer and a nitrogen inlet tube, deionized water (100 g), one ofthe invention surfactants (1) to (7), (9) to (13) and (17) to (24) andthe comparative products 1 to 4 (2 g) and di-2-ethylhexylperoxycarbonate (0.2 g) were charged. After the autoclave was purged to7 kPa to eliminate oxygen, vinyl chloride monomer (100 g) was charged.The autoclave was heated to 57° C. under stirring at 500 rpm to conductpolymerization. The internal pressure of the autoclave was 0.8 MPa atthe time of the initiation of the polymerization. Seven hours after theinitiation of the polymerization, the internal pressure dropped to 0.4MPa so that at that point, the polymerization was terminated. Unreactedvinyl chloride monomer was purged, and the contents were taken out ofthe autoclave and then dewatered and dried.

<Particle Size Distribution>

Among the thus-obtained resin particles, the weight percentage of thosenot passing through a 250-mesh sieve (a wire screen of the Tyler meshstandard) was measured.

<Waterproofness Test>

A sol was prepared in accordance with the following formulation. The solwas then formed into a thickness of 0.5 mm, followed by heating at 190°C. for 10 minutes into a sheet. The sheet was immersed for 24 hours inwater of 23° C., and its light transmittance (%) was measured.

Resultant resin 50 parts Di(2-ethylhexyl) phthalate 30 parts Ba/Zn basedstabilizer 1 part<Thermal Stability Test>

With respect to each of the invention surfactants (1) to (7), (9) to(13) and (17) to (24) and the comparative products 1 to 4, the same solas that subjected to the waterproofness test was poured into analuminum-made mold. After the sol was left over for 30 minutes in a hotair atmosphere of 190° C., a change in color tone was ranked inaccordance with a 5-level grading scale ranging from “A” (small change)to “E” (large change).

TABLE 6 Particle size Waterproofness Thermal distribution (%) (%)stability Invention product 1 0.0 89 A 2 0.0 88 A 3 0.0 89 A 4 0.0 86 B5 0.0 87 A 6 0.0 86 A 7 0.0 85 A 9 0.0 87 A 10 0.0 85 A 11 0.0 84 A 120.0 86 A 13 0.0 87 A 17 0.0 88 A 18 0.0 88 A 19 0.0 86 A 20 0.0 87 B 210.0 89 A 22 0.0 90 B 23 0.0 88 A 24 0.0 87 A Comp. product 1 3.4 76 D 22.0 71 E 3 0.0 85 D 4 1.3 87 D

Example 7

With respect to each of the invention surfactants (1) to (24) and thecomparative products 1 to 4, solution polymerization of styrene wasconducted to determine its performance as a resin modifier. Concerningthe thus-obtained resin, tests were conducted in accordance with thebelow-described testing methods. As a blank, solution polymerization wasconducted without addition of any resin modifier. The results are shownin Table 7.

<Polymerization Process>

Into a similar reaction vessel as in Example 4, xylene (100 g) werecharged, and the interior of the system was purged with nitrogen gas. Ona side, a mixed solution of styrene (150 g), one of the inventionsurfactants (1) to (24) and the comparative products 1 to 4 (15 g),benzoyl peroxide (2 g) and di(tertiary butyl) peroxide (1 g) wasprepared. At a reaction temperature of 130° C., the mixed solution wascontinuously added dropwise into the reaction vessel over 2 hours.Further, a mixed solution of xylene (10 g), benzoyl peroxide (0.5 g) anddi(tertiary butyl) peroxide (0.5 g) was added dropwise, followed by areaction for 2 hours. The reaction mixture was then cooled to afford apolymer solution.

<Anti-Fogging Properties>

The polymer solution was coated on a glass plate to produce a polymerfilm of 0.2 mm in thickness. The contact angle (O) of water on thepolymer film was measured to rank its anti-fogging properties.

<Antistatic Properties>

The above-described polymer films were left over for 24 hours in anatmosphere of 20° C. and 50% R.H., and their surface resistivity valueswere measured.

<Persistency of Antistatic Properties and Anti-Fogging Properties>

The polymer films which had been tested for antistatic properties andanti-fogging properties as described above were wiped with water (50times) by water-soaked absorbent cotton. After left over for 30 minutesin an atmosphere of 20° C. and 35% R.H., their surface resistivityvalues and the contact angles of water on them were measured.

TABLE 7 Surface Contact angle (°) resistivity (Ω) Before wiped Afterwiped Before wiped After wiped with water with water with water withwater Invention product 1 22.5 31.6 4.8 × 10¹⁰ 9.4 × 10¹⁰ 2 24.7 27.82.8 × 10¹¹ 5.0 × 10¹¹ 3 30.1 31.8 7.8 × 10¹⁰ 2.0 × 10¹¹ 4 28.3 28.7 5.5× 10¹⁰ 1.0 × 10¹¹ 5 29.4 30.6 1.3 × 10¹¹ 2.8 × 10¹¹ 6 21.5 32.2 3.9 ×10¹⁰ 7.8 × 10¹⁰ 7 22.2 34.1 6.4 × 10¹⁰ 5.5 × 10¹¹ 8 29.0 31.4 2.4 × 10¹⁰5.3 × 10¹⁰ 9 30.8 37.5 2.6 × 10¹¹ 3.8 × 10¹¹ 10 31.1 32.2 7.1 × 10¹⁰ 3.0× 10¹¹ 11 29.3 30.7 4.5 × 10¹⁰ 1.3 × 10¹¹ 12 29.8 33.6 1.1 × 10¹¹ 2.6 ×10¹¹ 13 27.5 30.2 3.7 × 10¹⁰ 6.8 × 10¹⁰ 14 32.2 38.1 5.4 × 10¹⁰ 5.9 ×10¹¹ 15 29.5 33.6 3.8 × 10¹⁰ 7.4 × 10¹⁰ 16 26.5 33.6 4.9 × 10¹⁰ 9.7 ×10¹⁰ 17 31.1 32.1 5.3 × 10¹⁰ 8.2 × 10¹⁰ 18 30.7 31.9 1.2 × 10¹¹ 1.5 ×10¹¹ 19 29.9 34.2 3.3 × 10¹⁰ 6.2 × 10¹⁰ 20 30.1 33.8 8.9 × 10¹⁰ 1.1 ×10¹¹ 21 28.9 32.2 5.9 × 10¹⁰ 7.9 × 10¹⁰ 22 27.5 31.9 6.5 × 10¹⁰ 8.8 ×10¹⁰ 23 28.8 33.1 4.4 × 10¹⁰ 8.3 × 10¹⁰ 24 29.2 31.8 3.7 × 10¹⁰ 5.9 ×10¹⁰ Comp. product 1 54.6 71.2 2.8 × 10¹¹ 3.9 × 10¹⁴ 2 49.9 86.2 5.0 ×10¹⁰ 6.9 × 10¹⁴ 3 36.4 40.0 1.3 × 10¹¹ 2.7 × 10¹² 4 31.5 43.2 3.9 × 10¹⁰7.8 × 10¹¹ Blank 98.3 98.5 1.0 × 10¹⁶ 1.0 × 10¹⁶

Industrial Applicability

As an advantageous effect, the present invention provides surfactants,which do not contain any phenyl ether group considered to havesignificant effects on the environment, such as a nonylphenyl group, andhave performance comparable with reactive surfactants containing one ormore phenyl ether groups.

1. A surfactant represented by the following formula (1):

wherein R¹ represents a branched aliphatic hydrocarbon group, or abranched aliphatic acyl group, which branched aliphatic hydrocarbongroup or branched aliphatic acyl group has 8 to 36 carbon atoms andcontains at least three methyl groups, AO and AO′ each independentlyrepresents an oxyalkylene group having 2 to 4 carbon atoms, L representsa group represented by formula (2) to be described below, z stands for anumber of from 1 to 10, X represents a hydrogen atom or an ionichydrophilic group, m stands for a number of from 0 to 1,000, and nstands for a number of from 0 to 1,000;

wherein R² and R³ each independently represents a hydrogen atom or amethyl group, x stands for a number of from 0 to 12, and y stands for anumber of 0 or
 1. 2. A surfactant according to claim 1, wherein informula (1), X represents an anionic hydrophilic group.
 3. A surfactantaccording to claim 2, wherein in formula (1), wherein X is an anionichydrophilic group represented by —SO₃M, —R⁴—SO₃M, —R⁵—COOM, —PO₃M₂, —PO₃MH or —CO—R⁶—COOM in which M represents a hydrogen atom, an alkali metalatom, an alkaline earth metal atom or an ammonium ion with a provisothat the number of M is ½ where M is an alkaline earth metal atom, R⁴and R⁵ each independently represents an alkylene group, and R⁶represents a residual group obtained by eliminating carboxyl groups froma dibasic acid or an anhydride thereof.
 4. A surfactant according toclaim 1, wherein in formula (1), X is a cationic hydrophilic group.
 5. Asurfactant according to claim 4, wherein in formula (1), X is a cationichydrophilic group represented by —R⁷—NR⁸R⁹R¹⁰Y or -Z-NR⁸R⁹R¹⁰—Y in whichR⁷ represents an alkylene group, R⁸ to R¹⁰ each independently representsan alkyl group having 1 to 4 carbon atom, an alkanol group having 2 to 4carbon atoms or a benzyl group, Y represents a halogen atom or amethylsulfuric group, and Z represents a group represented by—CH₂CH(OH)CH₂— or —CH(CH₂OH)CH₂—.
 6. A surfactant according to claim 1,wherein in formula (1), z is a number of from 1 to
 8. 7. A surfactantaccording to claim 2, wherein in formula (1), z is a number of from 1 to8.
 8. A surfactant according to claim 3, wherein in formula (1), z is anumber of from 1 to
 8. 9. A surfactant according to claim 4, wherein informula (1), z is a number of from 1 to
 8. 10. A surfactant according toclaim 5, wherein in formula (1), z is a number of from 1 to
 8. 11. In aprocess for emulsion polymerization using an emulsifier, the improvementcomprising using the surfactant according to claim
 1. 12. In a processfor suspension polymerization using a dispersant, the improvementcomprising using the surfactant according to claim
 1. 13. A compositioncomprising a resin and a resin modifier, wherein the resin modifiercomprises a surfactant according to claim 1.